Buffer-free process cycle for CO2 sequestration and carbonate production from brine waste streams with high salinity

ABSTRACT

A method includes: (1) using a chelating agent, extracting divalent ions from a brine solution as complexes of the chelating agent and the divalent ions; (2) using a weak acid, regenerating the chelating agent and producing a divalent ion salt solution; and (3) introducing carbon dioxide to the divalent ion salt solution to induce precipitation of the divalent ions as a carbonate salt. Another method includes: (1) combining water with carbon dioxide to produce a carbon dioxide solution; (2) introducing an ion exchanger to the carbon dioxide solution to induce exchange of alkali metal cations included in the ion exchanger with protons included in the carbon dioxide solution and to produce a bicarbonate salt solution of the alkali metal cations; and (3) introducing a brine solution to the bicarbonate salt solution to induce precipitation of divalent ions from the brine solution as a carbonate salt.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No.62/680,987, filed Jun. 5, 2018, the contents of which are incorporatedherein by reference in their entirety.

STATEMENT OF GOVERNMENT SUPPORT

This invention was made with government support under Grant NumbersDE-FE0029825 and DE-FE0031705, awarded by U.S. Department of Energy. Thegovernment has certain rights in the invention.

TECHNICAL FIELD

This disclosure generally relates to a carbonation route for carbondioxide (CO₂) sequestration.

BACKGROUND

Mineralization is a safe, long-term, stable, and environmentallyfriendly method for CO₂ sequestration. However, economically viablemineralization is challenging due to the large amounts of chemicalsincluded for pH swing and energy consumed during the process. Therefore,sustainable processes featuring streamlined operation, high yield, andreduced chemical use, and from which valuable products can bederived—hence offsetting operational costs—are highly desired for CO₂capture and storage.

It is against this background that a need arose to develop theembodiments described herein.

SUMMARY

In some embodiments, a method includes: (1) using a chelating agent,extracting divalent ions from a brine solution as complexes of thechelating agent and the divalent ions; (2) using a weak acid,regenerating the chelating agent and producing a divalent ion saltsolution; and (3) introducing carbon dioxide to the divalent ion saltsolution to induce precipitation of the divalent ions as a carbonatesalt.

In additional embodiments, a method includes: (1) combining water withcarbon dioxide to produce a carbon dioxide solution; (2) introducing anion exchanger to the carbon dioxide solution to induce exchange ofalkali metal cations included in the ion exchanger with protons includedin the carbon dioxide solution and to produce a bicarbonate saltsolution of the alkali metal cations; and (3) introducing a brinesolution to the bicarbonate salt solution to induce precipitation ofdivalent ions from the brine solution as a carbonate salt.

Other aspects and embodiments of this disclosure are also contemplated.The foregoing summary and the following detailed description are notmeant to restrict this disclosure to any particular embodiment but aremerely meant to describe some embodiments of this disclosure.

BRIEF DESCRIPTION OF THE DRAWINGS

For a better understanding of the nature and objects of some embodimentsof this disclosure, reference should be made to the following detaileddescription taken in conjunction with the accompanying drawings.

FIG. 1. A schematic of a process cycle for CO₂ sequestration andcarbonate production.

FIG. 2. Representative ethylenediaminetetraacetic acid (EDTA) complexconcentrations in a brine solution as a function of pH, as calculatedusing the chemical equilibrium software Visual MINTEQ 3.1. The logarithmof the concentration (log C), in molarity, represents the concentrationof metal complex species of Ca, Mg, and Na, with EDTA. The complexesremain stable at neutral and alkaline pH conditions typical of producedwater. As pH decreases, the concentrations of the different complexesrapidly decrease due to the precipitation of an acidic EDTA salt. Theconcentration of the EDTA complex with the monovalent Na⁺ ions isnegligible compared to the complexes with divalent ions. This examplecalculation is for an open system at ambient temperature and pressure inwhich the initial EDTA, Ca, Mg, and Na concentrations are 0.01 M.

DETAILED DESCRIPTION

Brine waste streams can be an excellent medium and reactant for CO₂mineralization because of the amount of wastewater available and theconcentrations (e.g., about 100,000 ppm or more) of the divalent ions(e.g., Ca²⁺ and Mg²⁺) in these streams. For example, shale gasproduction is accompanied by the generation of a brine waste streamcalled “produced water” during hydraulic fracking. In 2014, the quantityof such waste brine is more than about 22 billion barrels in the UnitedStates, offering substantial storage capacity for CO₂. Althoughtreatment and reuse of produced water is constrained by its highsalinity (e.g., about 400,000 ppm), selective extraction of divalentions like Ca²⁺ and Mg²⁺ contained in the waste stream can allowsubsequent CO₂ mineralization and production of carbonate salts (e.g.,CaCO₃, MgCO₃, and their related forms). However, the carbonation processis challenged by the relatively low concentrations of divalent ions(e.g., Ca²⁺ and Mg²⁺) in the brine. Therefore, an operationally stableand environmentally acceptable method of enrichment of such divalentions is desired to improve the carbonation process. One method ofdivalent metal extraction entails the use of recyclable materials (e.g.,chelating agents, metal oxide sorbents, and polymers with ion exchanginggroups) that can effectively uptake the desired ions from produced waterand be readily regenerated or recovered. In this cyclic protocol, wastestream generation is reduced, potentially allowing for the realizationof a zero-liquid-discharge system. As such, developing reliable methodsto enrich divalent ions from brine waste streams while recovering andrecycling the reaction precursors is desired in the practice of CO₂mineralization.

Some embodiments of this disclosure are directed to a process cycle toseparate and enrich divalent cations such as Ca²⁺ and Mg²⁺ from highsalinity brine solutions for CO₂ mineralization without requiring theuse of an alkaline buffer. The process cycle includes three interlinkedstages (shown in FIG. 1): (1) divalent ion extraction with a chelatingagent and membrane filtration; (2) regeneration of the chelating agentusing a weak acid (e.g., to a pH of about 2 or lower); and (3)production of carbonates following CO₂ injection, and recovery of theweak acid. By designing an integrated process, the use of expensiveconsumable chemicals is reduced through continuous recycling of therelevant reagents. The process cycle is also advantageous in the aspectof energy consumption because it does not involve energy-intensivestages such as electrolysis or temperature swing.

1) Divalent Ion Extraction from Brines

In this stage, divalent ions (or other multivalent ions) with potentialfor carbonation (e.g., those that can form carbonate solids by reactingwith CO₂) in a brine solution are enriched and then separated from thesolution. This is achieved by adding or introducing a chelating agent,such as ethylenediaminetetraacetic acid (EDTA) or nitrilotriacetic acid(NTA), into the brine solution under ambient conditions to promote theircomplexation with the target ions (e.g., Ca²⁺ and Mg²⁺), as given by:M ²⁺+EDTA→M ²⁺−EDTA  (1)where M denotes divalent ions, and EDTA is given as an example reagent.Other chelating agents that can form aqueous complexes via coordinationbonds with divalent ions, such as other polydentate chelating agents,can also be used. It is desired to select an appropriate chelating agentto selectively extract target divalent ions from high salinity brinesbecause of the high concentrations of alkali metal chlorides presentedin the high salinity brines. For instance, brines obtained fromdesalination of sea water and treatment of produced water are rich insodium chloride (NaCl). When EDTA is used, Ca²⁺ and Mg²⁺ can beselectively extracted because of EDTA's stronger preference forcomplexation with divalent ions compared to monovalent ions (e.g., Nat),as shown in FIG. 2. The Ca²⁺- and Mg²⁺-EDTA complexes have larger sizes,and thus can be readily separated using membrane filtration, such asthrough ultrafiltration (e.g., a polysulfone ultrafiltration unit with apore size from about 10 nm to about 100 nm) or nanofiltration (e.g., ananofiltration unit with a pore size from about 1 nm to about 10 nm). Amembrane filtration unit can be operated in a cross-flow modecontinuously to concentrate the Ca²⁺- and Mg²⁺-EDTA complexes in aretentate while monovalent ions (e.g., Na⁺, K⁺, and Cl⁻) permeatethrough the membrane pores. The retentate solution, which is thencollected, is thus enriched with Ca²⁺ and Mg²⁺ in the form EDTAcomplexes in an aqueous phase so that the volume of liquid can bereduced by about 10 to about 100 times. The significant reduction in theliquid volume to be handled can significantly lessen the energy andchemical use in the subsequent stages of the process.

2) Regeneration of Chelating Agent with Weak Acid

In the next stage, the chelating agent is recycled from the enricheddivalent ion solution by acidification. In the case of EDTA, themechanism is described by the following reaction:M ²⁺−EDTA+H ₂ ²⁺−EDTA(s)+MA ₂  (2)

In this reaction, a weak acid (HA) is added or introduced into, orotherwise combined with, the solution to precipitate EDTA as solidparticles (EDTA(s)) while the divalent ions remain in an aqueous form asdissolved salts (MA₂). As shown in FIG. 2, the concentrations of aqueousEDTA complexes begin to decrease as the solution is acidified to a pH ofabout 4 or lower due to the precipitation of EDTA solids. Unlike otherEDTA regeneration processes wherein strong acids, such as hydrochloricacid, are used, the process cycle uses a weak acid, so that theresulting divalent ion salt solution (MA₂) can further be treated toproduce carbonates and to regenerate the weak acid. When an acidstronger than carbonic acid is used, carbonation to regenerate such acidis generally not thermodynamically favorable. Options of such weak acidsinclude acetic acid, formic acid, lactic acid, oxalic acid, anotherorganic acid, or other acids having a pK_(a) greater than about 3.6 at298 K, such as about 3.7 or greater, about 3.8 or greater, about 3.9 orgreater, about 4 or greater, about 4.3 or greater, about 4.5 or greater,or about 4.7 or greater, and up to about 8 or greater, up to about 10 orgreater, or up to about 12. A concentrated solution of such weak acid isused to acidify the M²⁺-EDTA solution obtained from stage (1). Forinstance, acetic acid can be used to achieve a pH of about 1 to about 3(e.g., about 2), under which conditions the level of EDTA recovery canreach about 50%. After the precipitation reaction, the EDTA in solidform can be separated from the solution using a solid-liquid separationmethod, such as filtration or sedimentation/clarification. The collectedEDTA is recycled for divalent ion extraction in stage (1), while thesalt solution containing the divalent ions is transferred to acarbonation reactor as an input or a feed stream.

3) Carbonation Process and Acid Recovery

In this stage, the concentrated divalent ion salt solution (MA₂) fromstage (2) is first diluted with a mixture of treated brine in stage (1)and fresh water to a predetermined concentration based on the type ofweak acid used in stage (2) and the CO₂ concentration in a gas stream.The starting concentration of MA₂ in the diluted solution is adjusted sothat the solution pH is above the value (above about 3.6) of a carbonicacid solution in equilibrium with the CO₂-containing gas stream. Tofurther increase the pH for favorable precipitation of carbonates, theweak acid (e.g., acetic acid) can be separated from the concentrateddivalent ion salt solution via distillation. The gas stream is theninjected or introduced into the carbonation reactor (e.g., astirred-tank reactor) containing the diluted solution to precipitatecarbonates, as given by:MA ₂ +CO ₂ +H ₂ O→MCO ₃(s)+2HA  (3)

As an example, acetic acid can be used in stage (2) as it is a weakeracid (acid dissociation constant pK_(a) of about 4.76 at 298 K) thancarbonic acid (pK_(a) of about 3.6 at 298 K). Thus, carbonates of thedivalent ions (MCO₃(s)) are precipitated while the weak acid (HA) isregenerated in the solution. Higher conversion of MCO₃ can be achievedby increasing the CO₂ partial pressure to increase the concentration ofdissolved carbon in the liquid, for example, through CO₂ enrichment orapplication of elevated pressure (e.g., above ambient pressure and up toabout 30 bar to about 40 bar) to the gas stream. In addition, whenco-located with a thermal power plant as the CO₂ source, waste heat fromthe power plant can be harvested to increase the temperature of thecarbonation process to above about 45° C., at which condition theprecipitation of carbonates becomes strongly stimulated by boththermodynamics and kinetics. Under such conditions, carbonate conversioncan reach to about 70% to about 80%. As the injected CO₂ is mineralized,the produced carbonates can be collected by separating the precipitatesfrom the liquid using filtration. It should be noted that the pH of theweak acid solution (e.g., about 4 to about 5) at the end of this stageshould be above the pH of the carbonic acid solution. The acid solutionremaining in the reactor is then concentrated and reused in stage (2).The concentration can be performed by a process such as distillation andsolvent extraction, although nanofiltration is desirable to reduce theoperating cost.

A variation of the buffer-free process cycle involves the use of aregenerable natural or synthetic ion exchanger. In particular, aCO₂-enriched solution is produced by, for example, injecting orintroducing a CO₂-containing gas stream into water (or a brine solutionor another solution), and increasing the concentration of dissolvedcarbon in the solution through CO₂ enrichment or application of elevatedpressure (e.g., above ambient pressure and up to about 30 bar to about40 bar) to the gas stream. An ion exchanger is then added or introducedinto, or otherwise combined with, the CO₂-enriched solution to promoteion exchange, in which protons (H⁺) included in the CO₂-enrichedsolution are exchanged with alkali metal cations (e.g., N⁺, where N⁺ isNa⁺, K⁺, and so forth) included within the ion exchanger, producing abicarbonate salt solution (NHCO₃ ²⁻). Examples of suitable ionexchangers include heterogeneous ion exchangers, such aspolymer-supported ion exchangers in a particulate form of ion exchangepolymer beads including functional groups that can form complexes withexchangeable cations. Additional examples of heterogeneous ionexchangers include silicate minerals (e.g., a clay or a zeolite)supporting ion exchange reactions. Next, a divalent ion solution (e.g.,a brine solution) is added or introduced into, or otherwise combinedwith, the bicarbonate salt solution, inducing precipitation ofcarbonates of the divalent ions (MCO₃(s)). The divalent ion solution canbe an untreated brine solution or can be a concentrated divalent ionsolution (e.g., the concentrated divalent ion salt solution (MA₂) fromstage (2)). The heterogeneous ion exchanger can be removed from thesolution by filtration and then regenerated effectively by itssubsequent exposure to an alkali metal cation solution (e.g., a brinesolution).

Embodiments of this disclosure provide a sustainable process cycle forCO₂ sequestration and production of carbonates using brines. The brinescan be obtained as waste streams from industrial operations such asdesalination or treatment of produced water generated from oil and gasextractions. The process cycle can be operated as a CO₂ capture methodin post-combustion flue gas treatment to reduce the carbon emissions ofcoal-fired power plants. In addition, the process cycle also producescarbonates that can be used in construction, chemical, paper,sealants/adhesives, cosmetics, pharmaceutical, and food industries.

Advantages of the process cycle of some embodiments include:

1) It is an integrated process to simultaneously mineralize CO₂ andpretreat waste brines for further treatment.

2) Compared with other mineralization processes which use alkalinesolids (e.g., serpentine, slag and fly ash), the process cycle isadvantageous because the amount of brine available allows for therealization of CO₂ sequestration at a gigaton scale while omittingenergy-intensive operations of material pre-treatment, such as grinding,milling, and heat-treatment. In addition, the process cycle generatesvaluable products, namely carbonate salts, which have a wide range ofindustrial applications.

3) Other carbonation processes of seawater or brines which do notfeature an enrichment stage involve large amounts of alkaline buffers,which is either expensive (e.g., NaOH) or is limited in supply (e.g.,alkaline wastes). In the process cycle of some embodiments, relevantreagents are recycled and reused. Also, the process cycle can omit anenergy-intensive stage such as electrolysis. As such, the process cyclecan substantially lower the operational cost of brine mineralization.

In summary, the proposed process cycle treats waste streams (e.g., bothCO₂ and brines) sustainably at a reduced chemical or energy use andwhile deriving valuable carbonate products. As such, operational costscan be significantly reduced. Furthermore, the treated water exhibits ahigh potential for reuse in agriculture, irrigation, and animalconsumption.

The following are example embodiments of this disclosure.

First Aspect

In an aspect according to some embodiments, a method includes: (1) usinga chelating agent, extracting divalent ions from a brine solution ascomplexes of the chelating agent and the divalent ions; (2) using a weakacid, regenerating the chelating agent and producing a divalent ion saltsolution; and (3) introducing carbon dioxide to the divalent ion saltsolution to induce precipitation of the divalent ions as a carbonatesalt.

In some embodiments, extracting the divalent ions includes introducingthe chelating agent to the brine solution, followed by subjecting thebrine solution to filtration.

In some embodiments, subjecting the brine solution to filtration isperformed by at least one of ultrafiltration, nanofiltration, or reverseosmosis.

In some embodiments, subjecting the brine solution to filtrationincludes producing a retentate solution including the complexes of thechelating agent and the divalent ions.

In some embodiments, a concentration of the divalent ions in theretentate solution is about 1.5 times or greater than a concentration ofthe divalent ions in the brine solution, such as about 2 times orgreater, about 5 times or greater, about 10 times or greater, about 20times or greater, about 50 times or greater, and up to about 100 timesor greater.

In some embodiments, regenerating the chelating agent includesintroducing the weak acid to the retentate solution to induceprecipitation of the chelating agent and to produce the divalent ionsalt solution.

In some embodiments, the weak acid has a pK_(a) greater than about 3.6at 298 K, such as about 3.7 or greater, about 3.8 or greater, about 3.9or greater, about 4 or greater, about 4.3 or greater, about 4.5 orgreater, or about 4.7 or greater, and up to about 8 or greater, up toabout 10 or greater, or up to about 12.

In some embodiments, regenerating the chelating agent includes adjustingthe pH of the retentate solution to about 4 or below, such as about 3.9or below, about 3.7 or below, about 3.5 or below, about 3.3 or below,about 3.1 or below, about 2.9 or below, about 2.7 or below, about 2.5 orbelow, about 2.3 or below, about 2.1 or below, about 2 or below, orabout 1 to about 3.

In some embodiments, the method further includes adjusting the pH of thedivalent ion salt solution to above about 3.6, prior to introducing thecarbon dioxide.

In some embodiments, introducing the carbon dioxide includes inducingprecipitation of at least one of calcium carbonate or magnesiumcarbonate, or other carbonates (e.g., barium carbonates) or otherrelated solids.

Second Aspect

In another aspect according to some embodiments, a method includes: (1)combining water with carbon dioxide to produce a carbon dioxidesolution; (2) introducing an ion exchanger to the carbon dioxidesolution to induce exchange of alkali metal cations included in the ionexchanger with protons included in the carbon dioxide solution and toproduce a bicarbonate salt solution of the alkali metal cations; and (3)introducing a brine solution to the bicarbonate salt solution to induceprecipitation of divalent ions from the brine solution as a carbonatesalt.

In some embodiments, the ion exchanger is a heterogeneous ion exchanger.

In some embodiments, the heterogeneous ion exchanger is apolymer-supported ion exchanger.

In some embodiments, the heterogeneous ion exchanger is a silicatemineral to support ion exchange reaction.

In some embodiments, the method further includes recovering theheterogeneous ion exchanger by filtration.

In some embodiments, the method further includes regenerating theheterogeneous ion exchanger by exposing the heterogeneous ion exchangerto an alkali metal cation solution.

As used herein, the singular terms “a,” “an,” and “the” may includeplural referents unless the context clearly dictates otherwise. Thus,for example, reference to an object may include multiple objects unlessthe context clearly dictates otherwise.

As used herein, the term “set” refers to a collection of one or moreobjects. Thus, for example, a set of objects can include a single objector multiple objects. Objects of a set also can be referred to as membersof the set. Objects of a set can be the same or different. In someinstances, objects of a set can share one or more commoncharacteristics.

As used herein, the terms “connect,” “connected,” and “connection” referto an operational coupling or linking. Connected objects can be directlycoupled to one another or can be indirectly coupled to one another, suchas via one or more other objects.

As used herein, the terms “substantially” and “about” are used todescribe and account for small variations. When used in conjunction withan event or circumstance, the terms can refer to instances in which theevent or circumstance occurs precisely as well as instances in which theevent or circumstance occurs to a close approximation. For example, whenused in conjunction with a numerical value, the terms can refer to arange of variation of less than or equal to ±10% of that numericalvalue, such as less than or equal to ±5%, less than or equal to ±4%,less than or equal to ±3%, less than or equal to ±2%, less than or equalto ±1%, less than or equal to ±0.5%, less than or equal to ±0.1%, orless than or equal to ±0.05%.

Additionally, concentrations, amounts, ratios, and other numericalvalues are sometimes presented herein in a range format. It is to beunderstood that such range format is used for convenience and brevityand should be understood flexibly to include numerical values explicitlyspecified as limits of a range, but also to include all individualnumerical values or sub-ranges encompassed within that range as if eachnumerical value and sub-range is explicitly specified. For example, arange of about 1 to about 200 should be understood to include theexplicitly recited limits of about 1 and about 200, but also to includeindividual values such as about 2, about 3, and about 4, and sub-rangessuch as about 10 to about 50, about 20 to about 100, and so forth.

While the disclosure has been described with reference to the specificembodiments thereof, it should be understood by those skilled in the artthat various changes may be made and equivalents may be substitutedwithout departing from the true spirit and scope of the disclosure asdefined by the appended claims. In addition, many modifications may bemade to adapt a particular situation, material, composition of matter,method, operation or operations, to the objective, spirit and scope ofthe disclosure. All such modifications are intended to be within thescope of the claims appended hereto. In particular, while certainmethods may have been described with reference to particular operationsperformed in a particular order, it will be understood that theseoperations may be combined, sub-divided, or re-ordered to form anequivalent method without departing from the teachings of thedisclosure. Accordingly, unless specifically indicated herein, the orderand grouping of the operations are not a limitation of the disclosure.

What is claimed is:
 1. A method comprising: combining water with carbon dioxide to produce a carbon dioxide solution; introducing an ion exchanger to the carbon dioxide solution to induce exchange of alkali metal cations included in the ion exchanger with protons included in the carbon dioxide solution and to produce a bicarbonate salt solution of the alkali metal cations; and introducing a brine solution to the bicarbonate salt solution to induce precipitation of divalent ions from the brine solution as a carbonate salt.
 2. The method of claim 1, wherein the ion exchanger is a heterogeneous ion exchanger.
 3. The method of claim 2, wherein the heterogeneous ion exchanger is a polymer-supported ion exchanger.
 4. The method of claim 2, wherein the heterogeneous ion exchanger is a silicate mineral to support ion exchange reaction.
 5. The method of claim 2, further comprising recovering the heterogeneous ion exchanger by filtration.
 6. The method of claim 5, further comprising regenerating the heterogeneous ion exchanger by exposing the heterogeneous ion exchanger to an alkali metal cation solution. 